Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
  • C01B33/146—After-treatment of sols
  • C01B33/149—Coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
  • C01B33/146—After-treatment of sols
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
  • C01G1/02—Oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3081—Treatment with organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
  • C01P2004/12—Particle morphology extending in one dimension, e.g. needle-like with a cylindrical shape
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/14—Pore volume
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/16—Pore diameter
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/16—Pore diameter
  • C01P2006/17—Pore diameter distribution
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

• the present invention relates to a sol of a fine-grained or inorganic porous substance, a method for synthesizing the same, an application thereof, and an ink jet printing method using the sol, and an ink jet recording paper, a sheet, a film, a cloth, etc.
• the present invention relates to an ink jet recording medium coating liquid used for the production of the medium. Background technology>
• Inorganic fine particles are mainly produced by a gas phase method or a liquid phase method, and oxide fine particles such as aerosil-colloidal silica and metal fine particles such as gold colloid are known. Many of them are dense particles with no pores inside.
• inorganic amorphous porous substances include gel-like substances such as silica gel and alumina gel having pores in the gaps between particles, and amorphous activated carbon, but generally have a large particle diameter. .
• Japanese Patent Publication No. 4-70255 discloses porous spherical silica fine particles, which have an irregular pore shape with a small pore diameter. Chem. Lett., (2000) 1044, Stu. Sur. Sci. Catal., 129 (2000) 37, Japanese Patent Application Laid-Open No. 2000-1109312, etc. Although inorganic porous fine particles are shown, a precipitate was obtained in each case, and no sol in which the fine particles were dispersed was obtained.
• Japanese Patent Application Laid-Open No. 11-2010 discloses a rod-shaped mesoporous powder having a large aspect ratio, but using a cationic surfactant, a metal silicate, and an acid.
• US Pat. No. 6,096,696 describes a porous sol synthesized using a template. However, in the examples, the template is not removed and the porous sol is not realized.
• W002 / 00550 discloses a porous fine particle sol, but does not describe an aspect ratio or a degree of aggregation.
• the ink jet recording method is being used in a wide range of fields because of its low noise during recording, easy colorization, and high-speed recording.
• high-quality paper used for general printing has poor ink absorbency and drying properties, and has poor image quality such as resolution.Therefore, special papers that have improved these properties have been proposed.
• a recording paper coated with various inorganic pigments, such as amorphous silica, has been disclosed in order to increase the printing power. (Japanese Patent Laid-Open Nos. 555-15853, 55-148585, etc.)
• V and recording media have also been updated. Therefore, satisfactory performance is not always obtained with the above technology alone.
• insufficient ink absorption and bleeding due to an increase in the amount of ink ejected per unit area of the recording medium in order to obtain high image quality comparable to that of silver halide photography are raised.
• the transparency of the ink absorbing layer is also required to achieve high image quality and color density comparable to silver halide photography.
• Japanese Patent Application Laid-Open No. H10-163679 discloses an ink jet paper using inorganic fine particles having a high aspect ratio, but uses nonporous fine particles on a flat plate. Ink absorption tends to be inferior to porous ones.
• Japanese Patent Application Laid-Open Nos. 10-32 9406 and 10-1616615 disclose recording sheets using silica particles linked on a rosary, which are used here. Some silica particles are non-porous and tend to have lower ink absorption than porous ones.
• the present invention provides an inorganic porous material having a small particle size, a uniform pore size, a sol thereof, and a method for synthesizing the same. Further, the present invention provides an ink-jet recording medium having excellent ink absorption, transparency, water resistance, and light resistance, and a coating liquid for an ink-jet recording medium, in particular, using the same.
• the present invention is as follows.
• the average particle diameter of the particles measured by the dynamic light scattering method is 10 to 400 nm, 8
• a method for producing a sol containing an inorganic porous substance comprising: adding a metal source to a template solution or adding a template solution to a metal source in the mixing step; A method for producing a sol containing an inorganic porous material.
• the template is a nonionic surfactant represented by the following structural formula (1), and the weight ratio of the solvent to the weight of the template (solvent / template) is in the range of 10 to 1,000, and the metal source and The production method according to (16), wherein the template and the solvent are mixed.
• RO (C 2 H 4 O) a- (C 3 H 6 O) b- (C 2 H 4 O) 0 R (1) (where a and c are 10 to 1 10 respectively, and b is 30 to 70, R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms)
• the weight ratio of the template relative to S i 0 2 conversion weight of active silica as the metal source is in the range of 0.0 to 30 (1 3) - (1 7 )).
• An ink jet comprising a support and at least one ink absorbing layer provided on the support, wherein at least one of the ink absorbing layers contains the porous substance according to (12). recoding media.
• the average particle diameter of the particles measured by the dynamic light scattering method is 10 to '400 nm
• the average aspect ratio of the primary particles is 2 or more
• the mesopores are elongated in the longitudinal direction.
• the mesopore refers to a pore having a diameter of 2 to 50 nm
• the longitudinal direction refers to a direction of a larger value among the average particle diameter and the average particle length of the primary particles.
• the secondary aggregation in the present invention refers to a state in which primary particles are connected and / or strongly aggregated, and is in a state that cannot be easily dispersed in the primary particles.
• the presence or absence of secondary aggregation can be determined by spraying a sufficiently diluted sol and observing with an electron microscope. If the number of primary particles / the total number of particles is 0/5 or more, it can be said that substantially no secondary aggregation has occurred.
• Porosity in the present invention means that pores are measured by a nitrogen adsorption method, and the pore volume is preferably 0.1 m 1 / g or more, more preferably 0.5 ml / g or more.
• Means that Average pore diameter of porous material (diameter is simply called diameter Sometimes. ) Is preferably, but not limited to, 6 nm or more, more preferably 6 to 30 nm, and still more preferably 6 to 18 nm. Although it depends on the application to be used, a large pore diameter is preferable because a substance having a large size can easily enter the pores and diffusion is fast. If the pores are small, moisture in the air or the like may block the pores and block the flow of substances into the pores, which is not preferable.
• an average pore diameter of 6 to 18 nm which is close to the size of the dye, is preferable in order to chemically retain / stabilize the dye in the ink.
• An excellent ink absorbing layer can be obtained.
• Having a uniform pore size means that the average pore size is ⁇ 5% of the pore size determined from the nitrogen adsorption isotherm and the total pore volume (pore size measurable by the nitrogen adsorption method is 50 nm or less). It refers to a porous substance whose 5% or more of the total pore volume is contained in the range of 0%. In addition, it can be confirmed by TEM observation that the pores are uniform.
• the average particle diameter (the diameter may be simply referred to as diameter) of the porous substance of the present invention measured by the dynamic light scattering method is preferably from 10 to 400 nm, more preferably from 10 to 3 nm. It is 100 nm, more preferably 10 to 200 nm.
• a transparent substance can be obtained if the particle diameter is 200 nm or less.
• the ink is used as an ink absorbing layer of an ink jet recording medium, a printed matter having good color development and high color density can be obtained because of high transparency. If it is larger than 200 nm, the transparency is lowered, and if it is larger than 400 nm, sedimentation is likely to occur when the sol concentration becomes high, which is not preferable depending on the use.
• the average aspect ratio in the present invention means a value obtained by dividing a large value by a small value among the average particle diameter and the average particle length of the primary particles.
• the average particle diameter and average particle length of the primary particles can be easily obtained by observation with an electron microscope.
• particles with an average primary particle ratio of 2 or more are more microscopic than particles with only an average smaller than 2. Is preferred because the particles are coarsely packed, so that a large amount of substance can be easily retained and diffusion is fast.
• ink penetration is further improved.
• the shape may be fibrous, needle-like, rod-like, plate-like, cylindrical, or the like, but from the viewpoint of ink absorbability, needle-like or rod-like is preferred.
• the difference between this value and the nitrogen adsorption specific surface area S B by the BET method S B — S L of 25 Om 2 / g or more indicates that the porous material particles are extremely porous. . If this value is small, the ability to absorb the substance inside becomes small. For example, when used as an ink absorption layer, the ink absorption amount becomes small.
• S B — S L is 1 50 It is preferred that: If this value is large, handleability may be degraded.
• a compound containing an organic chain can be bound to the porous substance of the present invention.
• the compound containing an organic chain include a silane coupling agent and an organic cationic polymer.
• the bond with an organic medium and the adhesiveness can be improved. Further, particles having excellent chemical resistance such as alkali resistance can be obtained. Furthermore, it is possible to produce a sol that is stable even when acidified or a cationic substance or an organic solvent is added and can withstand long-term storage.
• the silane coupling agent used is preferably represented by the following general formula (2).
• X is a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having 1 to 12 carbon atoms substituted with a quaternary ammonium group and / or an amino group, or a quaternary ammonium group. And / or a group in which a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with an amino group is linked by one or more nitrogen atoms, and R represents a hydrogen atom or a carbon atom having 1 to 12 carbon atoms.
• n is an integer of 1 to 3.
• R examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and an isohexyl group Xyl group, cyclohexyl group, And an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are most preferable.
• hydrocarbons having 1 to 12 carbon atoms in X include methyl, ethyl, propyl, isopropyl, butyl, isoptyl, cyclohexyl, and benzyl. Particularly preferred are a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and a benzyl group.
• quaternary ammonium group and a hydrocarbon group having 1 to 12 carbon atoms substituted with Z or an amino group include an amino group, an aminoethyl group, an amino group, an aminopropyl group and an aminoisopropyl group.
• Groups, an aminobutyl group, an aminoisobutyl group, an aminocyclohexyl group, an aminobenzyl group and the like, and an aminoethyl group, an aminopropyl group, an aminocyclohexyl group, and an aminobenzyl group are particularly preferable.
• a group in which a hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a quaternary ammonium group Z or an amino group is linked by one or more nitrogen atoms is the same as described above. Further, the number of nitrogen atoms connecting the hydrocarbon group which may be substituted with these quaternary ammonium groups and / or amino groups is preferably 1 to 4.
• Specific examples of the compound represented by the above general formula (2) include, for example, methyltriethoxysilane, ptinoletrimethoxysilane, dimethyldimethoxysilane, aminopropyltrimethoxysilane, (aminoethyl) aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoamino Propyldimethylethoxysilane, aminopropylmethylethoxysilane, aminobutyltriethoxysilane, 3- (N-styrylmethyl-1-aminoethylamino) -1-propyltrimethoxysilane hydrochloride, aminoethylaminomethylphenethyl Limethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, and the like can be exemplified.
• the amount of the silane coupling agent to be added is preferably 0.002 to 2, more preferably 0.01 to 0.7 as a weight ratio of the silane coupling agent / porous substance.
• the silane coupling agent contains a nitrogen atom
• the nitrogen atom occupies 0.1 to 10%, more preferably 0.1%, as the weight ratio (hereinafter referred to as content) in the dry weight of the porous material after the treatment. 3-6% is good. If the content is too low, it may be difficult to obtain the effects of the present invention. If the content exceeds 10%, workability or other industrialization may be lacking.
• a treatment method using a silane coupling agent it may be directly added to a sol containing a porous substance, or may be added after being dispersed in an organic solvent in advance and hydrolyzed in the presence of water and a catalyst.
• the treatment is preferably carried out at a temperature from room temperature to the boiling point of the aqueous dispersion for several minutes to several days, more preferably at 25 ° C. to 55 ° C. for 2 minutes to 5 hours.
• the organic solvent examples include alcohols, ketones, ethers, and esters. More specifically, for example, alcohols such as methanol, ethanol, propanol, and butanol, methyl ethyl ketone, and methyl isobutyl ketone Such as ketones, methylacetosolve, ethinoleserosonolev, propylene glycolonepropane / glycerol, glycolenes such as ethylene glycol, propylene glycol, hexylene glycol, and methyl acetate. Esters such as ethyl acetate, methyl lactate and ethyl lactate are used.
• the amount of the organic solvent is not particularly limited, but is preferably 1 to 500, more preferably 5 to 50 as a weight ratio of the organic solvent / the silane coupling agent.
• inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid
• organic acids such as acetic acid, oxalic acid, and toluenesulfonic acid
• compounds exhibiting basic properties such as ammonia, amine, and alkali metal hydroxide
• the amount of water required for the hydrolysis of the silane coupling agent is 0.5 to 50 mol, preferably 1 to 25 mol, per 1 mol of Si—OR group constituting the silane coupling agent. Is desirable. It is desirable that the catalyst is added in an amount of 0.01 to 1 mol, preferably 0.05 to 0.8 mol, per 1 mol of the silane coupling agent.
• the hydrolysis of the silane coupling agent is usually carried out under normal pressure, at the boiling point of the solvent used. 13448
• the temperature is lower than the boiling point, preferably about 5 to 10 ° C lower than the boiling point. However, when using a heat-resistant and pressure-resistant container such as an autoclave, the temperature can be higher than this temperature. .
• the organic cationic polymer when used as an ink absorbing layer of an ink jet recording medium, water resistance and bleeding resistance after recording are improved.
• the organic cationic polymer can be arbitrarily selected from known organic cationic polymers conventionally used for ink jet recording media.
• the organic cationic polymer is preferably a polymer having a quaternary ammonium base, particularly preferably a homopolymer of a monomer having a quaternary ammonium base or a copolymer having the same. Copolymers with one or more other monomers that can be polymerized, and particularly preferred are those having a weight average molecular weight of 200,000 to 100,000.
• the weight ratio of the organic cationic polymer to the porous substance is preferably in the range of 1/99 or more and 99/1 or less. More preferably, it is in the range of 10/90 to 90/10.
• a hydrated metal oxide such as hydrated aluminum hydroxide, hydrated zirconium hydroxide, or hydrated tin hydroxide, or a basic metal chloride such as basic aluminum chloride can be added.
• a hydrated metal oxide such as hydrated aluminum hydroxide, hydrated zirconium hydroxide, or hydrated tin hydroxide, or a basic metal chloride such as basic aluminum chloride.
• the weight ratio of the compound to the porous substance is preferably in the range of 1/99 or more and 5OZ50 or less. More preferably, it is in the range of 595 to 30/70.
• the zeta potential of the porous substance is preferably +1 O mV or more or -1 O mV or less. If the zeta potential of the particles is out of the above range, the electric repulsion between the particles is reduced, so that the dispersibility is deteriorated and sedimentation, aggregation, and the like are easily caused. Zeta potential also changes with pH. Depending on the metal source and solvent, charged additives can be added by using surface modification with silane coupling agents or controlling pH. However, it is possible to produce a sol that is stable even when stored for a long time.
• a porous substance in which beads are connected and / or branched in a bead shape can be obtained.
• beads that are connected and / or branched in a rosary shape can easily hold a large amount of substances and spread quickly because the particles are coarsely packed microscopically. Therefore, it is preferable.
• ink penetration is further improved.
• the acidic aqueous solution of the porous substance having a negative zeta potential is slowly added to the acidic aqueous solution of the porous substance having a positive zeta potential by modifying the surface of the silane coupling agent having an amino group with stirring.
• the weight ratio of the porous substance having a negative zeta potential to the porous substance having a positive zeta potential is preferably 0.01 to 0.2, more preferably 0.01 to 0.05. It is. If the weight ratio is 0.2 or more, aggregation or precipitation occurs, which may not be preferable.
• a calcium salt, a magnesium salt or a mixture thereof can be added to the porous substance of the present invention.
• the light resistance may be improved by suppressing the decomposition of the dye in the ink.
• the calcium salt, the magnesium salt, or a mixture thereof is preferably added as an aqueous solution.
• Calcium ⁇ beam salt added, the amount of magnesium salts or mixtures thereof, is preferably at least 1 5 0 0 ppm at C a 0, M g O or weight ratio as this both with respect to S i 0 2, more Preferably it is 150 to 850 ppm.
• the addition is preferably carried out with stirring, and the mixing temperature and time are not particularly limited, but are preferably 2 to 50 ° C and about 5 to 30 minutes.
• added calcium and magnesium salts include inorganic salts such as calcium or magnesium chloride, bromide, iodide, fluoride, phosphate, nitrate, sulfate, sulfamate, formate and acetate. Acid salts and organic acid salts. these The calcium salt and the magnesium salt may be used as a mixture. The concentration of these salts to be added is not particularly limited, and may be 2 to 2 0 weight 0/0 approximately. If the polyvalent metal component other than calcium and magnesium is contained in the aqueous colloid solution of silica together with the calcium salt and the magnesium salt, the production can be more preferably performed.
• polyvalent metals other than calcium and magnesium examples include divalent, trivalent or tetravalent metals such as palladium, zinc, titanium, strontium, iron, nickel and cobalt.
• the amount of the calcium salt, magnesium salt, etc. to be added is converted into the amount of Ca0, Mg ⁇ , etc., the amount of these polyvalent metal components is The metal oxide is preferably about 10 to 80% by weight.
• the porous material of the present invention may contain as little sodium, potassium or mixtures thereof as possible.
• the pore volume may decrease or the pore size may change when used at high temperatures.
• the porous material is silica
• the amount of Natoriumu, potassium or mixtures thereof to be contained, S i 0 2 with respect to sodium ⁇ beam, a weight ratio of 1 0 0 as both a force Riumu child 0 ppm or less is preferred. It is more preferably at most 200 ppm.
• sodium and potassium contained are chloride, bromide, iodide, fluoride, phosphate, nitrate, sulfate, sulfamate, formate, acetate of metal or sodium or potassium lime.
• the sol in the present invention is a colloid solution in which a liquid is used as a dispersion medium and the porous substance of the present invention is a dispersion.
• Any dispersion medium may be used as long as it does not cause precipitation.
• one or more mixed solvents of water, alcohols, glycols, ketones, and amides are used.
• the organic solvent can be changed depending on the application.
• the latent heat of vaporization is lower than that of water such as alcohols and ketones.
• the latent heat of vaporization here refers to the amount of energy absorbed by the solvent when it evaporates, and a low latent heat of vaporization means that the solvent is easily vaporized.
• alcohols lower alcohols such as ethanol and methanol are preferable, and among ketones, ethyl methyl ketone is preferable.
• a high boiling point solvent having a boiling point of 100 ° C. or more is preferable.
• ethylene glycol, ethylene glycol mono-propyl ether, dimethylacetoamide, xylene, n-butanol, and methyleneisobutyl ketone are preferable. preferable.
• the sol stabilizes alkali metal hydroxides such as NaOH, organic bases, NH 4 OH, low-molecular-weight polyvinyl alcohol (hereinafter referred to as low-molecular-weight PVA), and surfactants.
• it contains an agent.
• alkali metal hydroxides, NH 4 OH and organic bases are particularly preferred.
• a stabilizer is added to the sol because the porous substance can be stable for a long period of time without precipitation, gelation, or the like.
• the amount of the stabilizer to be added is preferably 1 ⁇ 10 4 to 0.15, more preferably 1 ⁇ 1 CT 3 to 0.10, more preferably 5 ⁇ , as a weight ratio of the porous material.
• a viscosity modifier may be included to adjust the viscosity of the sol.
• a viscosity modifier means a substance that changes the viscosity.
• a sodium salt, an ammonium salt or the like is preferable. Particularly preferably those selected from N a 2 S 0 3, Na 2 S 0 4, Na C l, any one or more of the NH 3 HC 0 3.
• the amount of the viscosity modifier to be added is preferably 5 ⁇ 10 15 to ⁇ 0.03 as the weight ratio of the viscosity modifier Z porous material, more preferably 1 ⁇ 1 CT 4 to 0.01, furthermore, preferably from 5 X 1 0- 4 ⁇ 5 X 10 one 3.
• the viscosity modifier is 5 X 10- 5 or less, less the effect of the change in viscosity, also not preferable as this impairing the storage stability of the sol increases the viscosity modifier is 0.03 or more but require more electrolytes.
• the concentration of the sol varies depending on the use, but is preferably from 5 to 30% by weight, and more preferably from 5 to 30% by weight. If the concentration is too low, it is economically disadvantageous, and when used for coating or the like, it has drawbacks such as difficulty in drying and is not preferred from the viewpoint of transportation. If the concentration is too high, the viscosity will increase and stability may decrease, which is not preferable.
• the sol of the present invention comprises a metal source comprising a metal oxide and Z or a precursor thereof and a metal source. It is preferably produced by a production method comprising a step of mixing a plate and water to produce a sol of a metal oxide / template composite, and a step of removing the template from the composite.
• the metal source used in the present invention is a metal oxide and / or a precursor thereof.
• the metal species alkaline earth metals such as silicon, group 2 magnesium and calcium, zinc, group 3 aluminum and aluminum , Rare earth, etc., group 4 titanium, zirconium, etc., group 5 phosphorus, vanadium, group 7 manganese, tellurium, etc., group 8 iron, cobalt and the like.
• the precursor include non-metal salts such as nitrates and hydrochlorides of these metals, organic acid salts such as acetates and naphthenates, organic metal salts such as alkylaluminum, alkoxides, and hydroxides. It is not limited to this as long as it can be synthesized by the synthesis method described later. Of course, these may be used alone or in combination.
• a precursor that repeats condensation or polymerization to finally form silica can be used as the precursor, and is preferably tetraethoxysilane, methyltriethoxysilane, dimethyltriethoxysilane, Alkoxide-active silica such as 2-bis (triethoxysilyl) ethane can be used alone or in combination.
• Activated silica is particularly preferred because of its low cost and high safety.
• the activated silica used in the present invention can be prepared by, for example, extracting water glass with an organic solvent or exchanging water glass with ion. For example, when water glass is prepared by contacting it with an H + type cation exchanger, it is industrially preferable to use No.
• a sulfonated polystyrene dibutylbenzene-based strongly acidic exchange resin for example, Amberlite IR-120B manufactured by Rohm & Haas Co., Ltd.
• an alkali aluminate can be added to the water glass.
• the amount of aluminum aluminate added is preferably such that the Si / A1 element ratio of the mixture of silica and alumina is 2 ° C to 150 ° C. More preferably, it is in the range of 300 to 1000.
• S i / A 1 If the element ratio is greater than 1500, precipitation tends to occur at higher concentrations. If the S i / A 1 element ratio is less than 200, pores may not be formed when the template is removed.
• sodium aluminate, potassium aluminate, lithium aluminate, primary ammonium aluminate, guanidine aluminate and the like can be used, but sodium aluminate is preferable.
• the Na / A1 element ratio in sodium aluminate is preferably from 1.0 to 3.0.
• Examples of the template used in the present invention include cationic, aionic, nonionic, amphoteric surfactants such as quaternary ammonium-based compounds, and amineamine oxides such as dodecylamine, tetradecylamine, hexadecylamine, and octadecylamine.
• Any template such as a neutral template may be used.
• a triblock system such as Adeka L.P.F.F.R series manufactured by Asahi Denka or polyethylene glycol such as Adeka PEG series manufactured by Asahi Denka is used.
• a nonionic surfactant such as an ethylenediamine-based type such as the Adekipronic TR series can be used.
• RO (C 2 H 4 ⁇ ) a — (C 3 H 60 ) b _ (C 2 H 40 ) c R (where a and c are 10 to 110, respectively)
• B represents 30 to 70, and R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• the structural formula HO (C 2 H 4 0) a — (C 3 H 6 0) b — (C 2 H 4 0) c H (where a and c are respectively 10 to 11 and ⁇ is 30 to 70) or the structural formula R (OCH 2 CH 2 ) n OH (where R is an alkyl group having 12 to 20 carbon atoms and n is 2 to 30) are preferred.
• Asahi Denka's pull port P 103 (HO (C 2 H 40 ) 17 — (C 3 H 6 O) 6 ._ (C 2 H 4 O) 17 H) ⁇ PI 2 3 (HO (C 2 H 4 O) 2 .1- (C 3 H 6 O) 7 .— (C 2 H 4 O) 2 .H), P 85, etc., polyoxyethylene, polyoxyethylene styrene, polyoxyethylene Noreate ⁇ ⁇ polyoxyethylene stearyl ether and the like.
• Aromatic hydrocarbons with 6 to 20 carbon atoms as organic auxiliaries to change pore size Element an alicyclic hydrocarbon having 5 to 20 carbon atoms, an aliphatic hydrocarbon having 3 to 16 carbon atoms, and a halogen-substituted product such as toluene, trimethylbenzene, triisopropylbenzene, etc. be able to.
• the reaction between the metal source and the template can be carried out, for example, by stirring and mixing a metal source dissolved or dispersed in a solvent and a template dissolved or dispersed in a solvent, but is not limited thereto. is not.
• a solvent any of water and a mixed solvent of water and an organic solvent may be used, and as the organic solvent, alcohols are preferable.
• alcohols lower alcohols such as ethanol and methanol are preferable.
• composition used in these reactions differs depending on the template, the metal source, and the solvent, but it is necessary to select a range in which aggregation or precipitation occurs and the particle diameter does not increase.
• an alkali such as NaOH or a stabilizer such as low molecular weight PVA may be added to prevent aggregation and precipitation of particles.
• a pH adjuster, a metal sequestering agent, a fungicide, a surface tension adjuster, a wetting agent, and a water-proofing agent may be added to the solvent within a range that does not cause aggregation or precipitation.
• the following composition can be used.
• P 1 23 / S i 0 2 weight ratio preferably 0.01 to 30, more preferably from 0.1 to 5 is used.
• the weight ratio of the organic auxiliary agent ZP123 is preferably from 0.02 to 100, more preferably from 0.05 to 35.
• the weight ratio of water / P123 at the time of the reaction is preferably from 10 to 1,000, more preferably from 20 to 500.
• a Na OH may be added at 1 X 1 0-4 ⁇ 0. 1 5 range as Na OH / / S i 0 2 weight ratio.
• a similar composition can be used when using the pull-mouth nick P 103.
• the mixing of the metal source, the template, and the solvent is preferably performed while stirring at 0 to 80 ° C, more preferably at 0 to 40 ° C.
• the addition time in the present invention refers to the addition of a metal source to a template solution or the addition of a metal source. It means the time required from the start to the end of the addition of the plate solution to the metal source.
• the addition time is preferably at least 3 minutes, more preferably at least 5 minutes. When the addition time is less than 3 minutes, the average aspect ratio of the primary particles becomes less than 2, and when used as an ink absorbing layer of an ink jet recording medium, the ink absorption amount may decrease.
• the addition time can be controlled by the addition rate of the metal source or template solution. If the addition rate is substantially constant, it is preferable because the reproducibility of the average aspect ratio and the average particle diameter of the primary particles is good, but it is not necessarily required to be constant.
• the reaction proceeds easily at room temperature, but can be carried out under heating up to 10 ° C if necessary. However, conditions such as a hydrothermal reaction of 10 ° C. or more are unnecessary.
• the reaction time ranges from 0.5 to 100 hours, preferably from 3 to 50 hours.
• the pH during the reaction is preferably in the range of 3 to 12, more preferably in the range of 6 to 11, and even more preferably in the range of 7 to 10. For example, if silicon is selected as the metal, adjusting the pH to 7 to 10 may shorten the reaction time.
• An alkali such as Na ⁇ H or ammonia or an acid such as hydrochloric acid, acetic acid, or sulfuric acid may be added to control the pH.
• aluminum aluminate may be added, but it may be at any time before or after the formation of the composite or after removing the template.
• the addition of alkali aluminate makes it possible to produce a sol that is stable even when acidified or a cationic substance is added and that can withstand long-term storage.
• alkali aluminate there can be used sodium aluminate, potassium aluminate, lithium aluminate, primary ammonium aluminate, guanidine aluminate, etc., and preferably sodium aluminate.
• the element ratio of Na / A1 in sodium aluminate is preferably from 1.0 to 3.0.
• the addition of the alkali aluminate solution is performed at 0 to 80 ° C, preferably 5 to 40 ° C. With stirring.
• the concentration of the aluminum aluminate to be added is not particularly limited, but is preferably used at 0.5 to 40% by weight, more preferably 1 to 20% by weight / 0 .
• the amount to be added is preferably 0.003 to 0.1 as an element ratio of A1 / (Si + A1), and more preferably. Is from 0.005 to 0.05.
• the mixture is preferably heated at 40 to 95 ° C, more preferably at 60 to 80 ° C.
• the obtained complex is separated by filtration or the like, washed with water, dried, and then the contained template is removed by a method such as contact with a supercritical fluid or a solvent such as alcohol, or calcination.
• a porous material may be obtained.
• the sintering temperature is not less than the temperature at which the template disappears, and is approximately 500 ° C. or more.
• the firing time is appropriately set depending on the temperature, but is about 30 minutes to 6 hours.
• a method of stirring and mixing the solvent and the complex, a method of packing the complex in a column or the like, and circulating the solvent can be used.
• a porous substance can be obtained by adding a solvent such as alcohol to the obtained reaction solution and removing the template from the composite.
• a solvent such as alcohol
• an ultrafiltration device because the porous substance can be handled as a sol.
• the ultrafiltration may be performed under pressure as well as under atmospheric pressure.
• materials for the membrane for ultrafiltration polysulfone, polyetherketone, polyacrylonitrile (PAN), polyolefin, cellulose and the like can be used, and the shape thereof is hollow fiber type, flat membrane type, spiral type, Any of tube type etc. is acceptable.
• the material of the ultrafiltration membrane is preferably a hydrophilic membrane such as a PAN membrane, a cellulose membrane, or a charged membrane.
• the charged membrane includes a positively charged membrane and a negatively charged membrane.
• a positively charged membrane a membrane in which a positively charged group such as a quaternary ammonium base is introduced into an organic polymer or an inorganic substance such as polysulfone, polyether sulfone, polyamide, or polyolefin is used. Examples thereof include a film in which a negatively charged group such as a carboxyl group and a sulfonic acid group is introduced into an organic polymer or an inorganic substance.
• alkali or small molecule P such as NaOH to prevent agglomeration of particles It may be added a stabilizer VA like, N a 2 S_ ⁇ 3 etc. Natoriumu salt and NH 3 HCO 3 such Yo also added viscosity modifier such Anmoyuumu salt.
• the solvent used for the removal may be any solvent that dissolves the template, and may be an organic solvent that is easy to handle and has a high dissolving power for the template.
• the pH of the sol when removing the template is preferably in the range of 7 to 12, more preferably in the range of pH 8 to 11.
• An alkali such as NaOH or ammonia or an acid such as hydrochloric acid, acetic acid or sulfuric acid may be added for controlling pH. If the pH is too high, the structure of the porous substance may be changed, and if the pH is too low, aggregation may occur.
• the removal temperature is preferably cooled below the micelle formation temperature of the template. Cooling below the micelle formation temperature causes the template to dissociate, making it easier to pass through the filtration membrane.
• the micelle formation temperature means a temperature at which the template starts forming micelles in a solution when the temperature is increased at an arbitrary concentration. The actual temperature varies depending on the solvent and template used, but is preferably 60 ° C. or lower, more preferably 0 to 20 ° C. If the temperature is too low, the solvent freezes and is undesirable.
• the porous substance is a metal oxide
• the surface hydroxyl groups react with the silane coupling agent, and the template is released from the composite. If the pH is adjusted near the isoelectric point (the absolute value of the difference from the isoelectric point is within 1.5), the electrical repulsion between the particles will be reduced, and the porous material will aggregate and centrifugal separation will occur.
• the template can be easily removed by filtration or filtration. When the pH is adjusted to a value apart from the isoelectric point after removing the template, a porous substance having an average particle diameter of substantially 100 to 400 nm, which is substantially not secondary aggregated, is obtained.
• the removed template can be reused by removing the solvent. Recycling can reduce the cost of raw materials industrially, as compared to removal by incineration. It does not generate heat due to incineration and does not waste resources, so it is suitable for solving environmental problems. Any method can be used as long as the template does not decompose.However, for example, the template solution removed by ultrafiltration or the like can be reused. It may be heated to a cell formation temperature or higher and concentrated by using an ultrafiltration membrane having a small molecular weight cut-off. The ultrafiltration membrane used at this time is preferably a hydrophilic membrane. Further, the solvent may be removed by distillation.
• distillation is more efficient and preferable than using ultrafiltration. Distillation can be performed by any method as long as precipitation or gelation does not occur, but vacuum distillation is preferred in terms of sol stability and distillation efficiency.
• the heating temperature when performing the distillation is preferably from 20 to 100 ° C, more preferably from 20 to 45 ° C.
• a rotary filter, a rotary evaporator, a thin film evaporator and the like can be used.
• Concentration by the distillation method may be performed alone or in combination with ultrafiltration. When used in combination with ultrafiltration, it may be performed before and / or after ultrafiltration, but is preferably performed after ultrafiltration because the solvent to be evaporated is reduced. Before the distillation, it is preferable to add a stabilizer or to treat the porous substance with a silane coupling agent or the like in order to prevent precipitation or gelation.
• methods such as heat drying, vacuum drying, spray drying, and supercritical drying can be used.
• porous substance and / or the sol of the porous substance of the present invention may be variously modified depending on the use.
• a metal such as platinum or palladium may be supported.
• the porous substance of the present invention has pores, it can be expected to absorb, wrap and protect the substance, and release it gradually.
• adsorption heat pump Adsorbents, humectants, catalysts, catalyst carriers, ink absorbents, pharmaceutical carriers used in drug delivery systems, cosmetics, foods, dye carriers, and the like.
• they since they are fine particles, they can be applied to fields that require transparency and smoothness.
• it can be used as a filler for rubber, resin, paper, a thickener for paint, a thixotropic agent, an anti-settling agent, an anti-blocking agent for films, and the like.
• the film since it is transparent, has pores, and has a low density, it can be used as a low refractive index film, an antireflection film, a low dielectric constant film, a hard coat film, a heat insulating material, a sound insulating material, and the like.
• a transparent and smooth film can be formed, and the film can be suitably used as a photographic ink jet recording medium by making use of a substance absorbing effect of pores.
• the ink jet recording medium is used as an ink jet recording medium.
• the pigment may be either a dye or a pigment
• the solvent may be an aqueous or non-aqueous solvent.
• the ink jet recording medium includes a support and at least one or more ink absorbing layers provided on the support. If necessary, two or more ink absorbing layers can be provided. In this way, by forming the ink absorbing layer into multiple layers, it is possible to share functions such as imparting gloss to the surface to each layer.
• the porous material of the present invention needs to be contained in at least one layer.
• the content of the porous "raw material" of the present invention is not particularly limited, but is preferably 10 to 99% by weight / 0 with respect to each ink absorbing layer containing the porous material.
• the content is preferably 1 to 99% by weight with respect to the entire absorbing layer, and if the content is too low, the ink absorbency is unfavorably reduced.
• an organic binder can be used as a binder that does not impair the ink absorption of the porous substance.
• PVA polybutyl alcohol
• polybutyl acetate polyvinyl pyrrolidone
• polyacetal polyurethane
• polybutyral poly (meth) acrylic acid (ester)
• polyamides polyacrylamides, polyester resins, urea resins, melamine resins, starch and starch derivatives derived from natural polymers, carboxymethylcellulose, hydroxyethyl, etc.
• Base derivatives casein, gelatin, latex, emulsion and the like.
• examples of the latex include a vinyl acetate polymer latex, a styrene-isoprene copolymer latex, a styrene-butadiene copolymer latex, a methyl methacrylate relay butadiene copolymer latex, an acrylate copolymer latex, and a copolymer of these.
• examples include a functional group-modified polymer latex obtained by modifying the union with a functional group-containing monomer such as a carboxyl group.
• PVA derivatives include cation-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and the like. Of course, these binders can be used in combination.
• the content of the organic binder used in the present invention is not particularly limited.
• polyvinyl alcohol when used, it is preferably contained in an amount of 5 to 400 parts by weight based on 100 parts by weight of the porous substance. It is particularly preferred that the content be contained in an amount of up to 100 parts by weight. If the content is small, the film-forming property is reduced, and if the content is large, the ink absorption is reduced, which is not preferable.
• the present invention also provides a coating liquid for an ink jet recording medium, comprising a component of an ink absorbing layer and a solvent.
• the solvent used is not particularly limited, but water-soluble solvents such as alcohols, ketones and esters, and Z or water are preferably used.
• a pigment dispersant, a thickener, a flow regulator, a defoaming agent, a defoaming agent, a release agent, a foaming agent, a coloring agent, and the like can be added to the coating solution as needed.
• At least one of the ink absorption layers contains a cationic polymer.
• the cationic polymer is not particularly limited as long as it shows cationicity. At least one of a primary amine, a secondary amine, a tertiary amine substituent and a salt thereof, or a quaternary ammonium salt substituent is used.
• the molecular weight of the cationic polymer is not particularly limited, but those having a weight average molecular weight of from 1,000 to 200,000 are preferably used.
• at least one of the ink absorbing layers contains an ultraviolet absorber, a hindered amine light stabilizer, a singlet oxygen quintin and an antioxidant. The light resistance of the printed portion is improved by containing the substance.
• the ultraviolet absorber is not particularly limited, but benzotriazole-based, benzophenone-based, titanium oxide, cerium oxide, zinc oxide and the like are preferably used.
• the hindered amine light stabilizer is not particularly limited, but the N atom of the piperidine ring is N—R (R is a hydrogen atom, an alkyl group, a benzyl group, an aryl group, an acetyl group, an alkoxyl group, a cyclohexyl group, and a benzyloxy group. ) Is preferably used.
• the singlet oxygen quencher is not particularly limited, but aniline derivatives, organic nickel compounds, spirochromane compounds, and spiroindane compounds are preferably used.
• the antioxidant is not particularly limited, but phenol-based, hydroquinone-based, organic thio-based, phosphorus-based, and amine-based antioxidants are preferably used.
• At least one of the ink absorbing layers preferably contains an alkaline earth metal compound.
• an alkaline earth metal compound improves light resistance.
• oxides, halides and hydroxides of magnesium, calcium and potassium are preferably used.
• the method for incorporating the alkaline earth metal compound into the ink absorbing layer is not particularly limited. It may be added to the coating liquid slurry, or may be added at the time of synthesizing the inorganic porous material or after the synthesis, and may be used after adhering.
• the amount of the alkaline earth metal compound used is preferably 0.5 to 20 parts by weight in terms of oxide based on 100 parts by weight of the inorganic porous material.
• the ink absorbing layers contains a nonionic surfactant.
• the image quality and light resistance are improved by containing a nonionic surfactant.
• the nonionic surfactant is not particularly limited, but higher alcohols, ethylene oxide adducts of carboxylic acids, and ethylene oxide-propylene oxide copolymers are preferably used, and ethylene oxide-propylene oxide copolymers are preferably used. Polymers are more preferably used.
• the method for incorporating the nonionic surfactant in the ink absorbing layer is not particularly limited.
• the coating liquid slurry may be added at the time of synthesizing the inorganic porous material or after the synthesis, and may be used after adhering.
• the alcohol compound is not particularly limited, but aliphatic alcohols, aromatic alcohols, polyhydric alcohols, and hydroxyl-containing oligomers are preferably used, and polyhydric alcohols are more preferably used.
• the method for incorporating the alcohol compound into the ink absorbing layer is not particularly limited. It may be added to the coating liquid slurry, or may be added at the time of synthesizing the inorganic porous material or after the synthesis, and may be used after adhering.
• At least one of the ink absorption layers contains alumina hydrate.
• alumina hydrate By containing alumina hydrate, image quality and water resistance are improved.
• the alumina hydrate is not particularly limited, and alumina hydrate having a boehmite structure, pseudo-boehmite structure, or amorphous structure is used, and alumina hydrate having a pseudo-boehmite structure is preferably used.
• At least one of the ink absorption layers contains colloidal silica and / or dry silicic acid.
• colloidal silica is not particularly limited, and examples thereof include ordinary anionic colloidal silica, and cationic colloidal silica obtained by a method of reacting a polyvalent metal compound such as aluminum.
• the fumed silica is not particularly limited, but fumed silica synthesized by burning silicon tetrachloride with hydrogen and oxygen is preferably used. Dry silica may be used as it is, or may be one whose surface is modified with a silane coupling agent or the like.
• a gloss layer can be provided as the outermost layer.
• the means for providing the glossy layer is not particularly limited, but a method for containing an ultrafine particle pigment such as colloidal silica and / or fumed silica, a super calendar method, a Daros calender method, a casting method and the like are used.
• the support used in the present invention is not particularly limited, but paper, a polymer sheet, a polymer film, and a cloth are preferably used. These supports may be subjected to a surface treatment such as corona discharge if necessary.
• the thickness of the ink absorption layer is particularly limited. However, the amount is preferably 1 to 100 ⁇ , and the coating amount is preferably 1 to 100 g / m 2 .
• the method of applying the coating liquid is not particularly limited, but a blade coater, an air knife coater, a lorno coater, a plus coater, a curtain coater, a no coater, a gravure coater, a sprayer and the like can be used.
• the pore distribution and specific surface area were measured with Nitrogen using Autosoap-11 manufactured by Qantachrome.
• the pore distribution was calculated by the BJH method.
• the average pore diameter was calculated from the peak value in the mesopore region of the differential pore distribution curve obtained by the BJH method.
• the specific surface area was calculated by the BET method.
• the average particle diameter and the zeta potential by the dynamic light scattering method were measured with a laser zeta potentiometer ELS-800 manufactured by Otsuka Electronics.
• the viscosity was measured at 25 ° C using Brookfield viscometer LVDV I 1+ and a small sample No. 21 for small sample volume.
• the TEM photograph was taken using Hitachi H_700.
• a film was formed using a bar coater, and then the center portion, which was 3 cm apart from the top and bottom, was measured at 10 places using a micrometer, and the film thickness was averaged.
• Pencil strength was used as a means for measuring film strength.
• the pencil is drawn with a pencil lead to check for tearing of the coating, and the pencil density symbol (6 to 9 mm) at the next lower level of the pencil where the tear is recognized is defined as the pencil hardness.
• the evaluation of the printing characteristics was carried out by performing solid printing of yellow, magenta, cyan, and black on the above coating film using a commercially available ink jet printer ((800C manufactured by Seiko Epson). Ink absorbency is determined by bleeding after printing Immediately after the character, the printed portion was pressed with blank paper, and the degree of ink transfer was determined.
• the water resistance was evaluated by dropping one drop of pure water on the printed portion of the coating film and determining the degree of bleeding and outflow after drying.
• the light resistance was evaluated by applying a xenon feedometer to the printed coating film.
• Tables 1 and 2 show the evaluation results of the coating films and sols of the following examples.
• Pluronic P123 100 g was dissolved in 8700 g of water, and 1200 g of the above aqueous activated silica solution was added at a constant addition rate in 10 minutes while stirring in a 35 ° C water bath.
• the pH of this mixture was 4.0.
• the weight ratio of water / P 123 is 98.4
• the weight ratio of P 123ZS i 0 2 1. is 67.
• the mixture was stirred at 35 ° C. for 15 minutes, and then allowed to stand at 95 ° C. and reacted for 24 hours.
• the average particle size of the sample in the sol (A) measured by the dynamic light scattering method was 20 O nm, and the converted specific surface area was 13.6 m 2 / g.
• the sol was dried at 105 ° C to obtain a porous material.
• the average pore diameter of this sample was 10 nm, and the pore volume was 1.1 1 ml Zg.
• the nitrogen adsorption specific surface area by the BET method was 540 m 2 Zg, and the difference from the reduced specific surface area was 526.4 m 2 / g.
• Observation of the primary particles of this sample from electron micrographs revealed that the primary particles were rod-shaped particles having an average particle diameter of 30 nm, an average particle length of 200 nm, and an average aspect ratio of 6.7.
• the obtained zonole (A) was used as a coating film, it was dried at room temperature in about 10 minutes to obtain a film having a thickness of 18.0 ⁇ 2.0 ⁇ and a pencil strength of HB.
• Example 2 was added N a OH aqueous 0.1 defined mixture of S i 0 2 and P 1 23 obtained in Example 1, the pH was adjusted to 9.5. After reacting for 3 hours with stirring at 65 ° C., the same operation as in Example 1 was performed, and a product equivalent to sol (A) was obtained.
• Example 2 To 100 g of the sol (A) obtained in Example 1, 0.41 g of a 10% by weight aqueous solution of calcium nitrate was added at room temperature with stirring. The pH after stirring at room temperature for 30 minutes was 9.9. Observation of the primary particles of this sample from electron micrographs revealed that about 10 rod-shaped particles with an average particle diameter of 30 nm and an average particle length of 200 nm were connected in a beaded shape on average. The obtained sol (B) was used as a coating film.
• Example 4 To 100 g of the sol (A) obtained in Example 1, 0.99 g of a 10% by weight aqueous solution of magnesium chloride was added at room temperature with stirring. The pH after stirring at room temperature for 30 minutes was 9.8. Observation of the primary particles of this sample from electron micrographs revealed that about 10 rod-shaped particles with an average particle diameter of 30 nm and an average particle length of 200 nm were connected in an rosary shape on average. The obtained sol (C) was used as a coating film.
• sol (D) was obtained when dispersed using an ultrasonic disperser. The pH was 2.1 and the zeta potential was 34 mV. The obtained sol (D) was used as a coating film.
• sol (E) was obtained by dispersion using an ultrasonic disperser.
• the zeta potential was -45mV.
• the obtained sol (E) was used as a coating film.
• sol (F) was used as a coating film.
• Example 8 To 100 g of the sol (D) obtained in Example 5, 3.0 g of the sol (A) obtained in Example 1 was slowly added while stirring. pH was 2.5. Observation of the primary particles of this sample from an electron micrograph showed that about 15 rod-shaped particles having an average particle diameter of 30 nm and an average particle length of 200 nm were connected in an rosary shape on average. The obtained sol (G) was used as a coating film.
• 100 g of the cationic polymer was added to 100 g of the sol (D) obtained in Example 5.
• / 0 a molecular weight of about 4 0 0 0 0 di ⁇ Lil dimethyl ammonium - a Umukuroraido polymer solution 7 g was added at room temperature under stirring. It was dispersed using an ultrasonic disperser to obtain a sol (H). pH was 2.2. The obtained sol (H) was used as a coating film.
• Example 2 20 g of the sol (A) obtained in Example 1 was mixed with 10 g of commercially available Koguchi idal silica (Snowtex N, manufactured by Nissan Kagaku) to obtain a sol (J).
• the obtained sol (J) was used as a coating film, it was dried at room temperature for about 10 minutes to obtain a film having a thickness of 18.0 ⁇ 1.5 ⁇ and a pencil strength of ⁇ .
• Example 2 Ethylene glycol was added to the sol ( ⁇ ) obtained in Example 1 so that the solvent contained 10% in the solvent, to obtain a sol ( ⁇ ).
• the viscosity of this solution was 450 ° C.
• this sol (K) was used as a coating film, it was dried at room temperature for about 120 minutes, and a film having a thickness of 20.0 ⁇ 0.5111 and a pencil strength of ⁇ ⁇ was obtained.
• the average particle size of the sample in this sol (M) measured by the dynamic light scattering method is 200 nm, and the converted specific surface area is 13. Met.
• the sol was dried at 105 ° C to obtain a porous material.
• the average pore diameter of this sample was 10 nm, and the pore volume was 1 ⁇ 10 mlZ.
• the nitrogen adsorption specific surface area by the BET method was 535 m 2 Zg, and the difference from the reduced specific surface area was 521.4 m 2 / g.
• Observation of the primary particles of this sample from electron micrographs revealed that the primary particles were rod-shaped particles having an average particle diameter of 30 nm, an average particle length of 200 nm, and an average aspect ratio of 6.7.
• the obtained sol (M) was used as a coating film, it was dried at room temperature for about 40 minutes to obtain a film having a thickness of 18.0 ⁇ 2.0 and a pencil hardness of HB. -
• Example 2 To the reaction solution obtained in Example 1, 17.4 g of 3_ (2-aminoethyl) aminopropyl trimethoxysilane was added with stirring. The pH of the mixture was 8.5. After stirring for 1 hour at 25 ° C, the reaction proceeded to pH 8.0 and aggregates were formed. After filtering the aggregate, 10 times the amount of water based on the weight of the aggregate was added and dispersed. After the aggregate was filtered again, 26.5 g of 6N hydrochloric acid was added. It was dispersed using an ultrasonic disperser, and a product substantially equivalent to the sol (D) prepared in Example 5 was obtained.
• the pull-out nick was concentrated in the same manner except that cellulose membrane C 03 OF (manufactured by Nadia) was used instead of KCP-1010. 70 minutes. Also, the amount of water permeability after cleaning is It recovered to almost the same level as before.
• the pH of this mixture was 3.5.
• the weight ratio of water / P 1 23 is 38.5
• the mixture was stirred at 35 ° C for 15 minutes, and then allowed to stand at 95 ° C and reacted for 24 hours.
• the solution using an ultrafiltration device removes the P 123 from to obtain a sol (O) of S i 0 2 concentration of about 7.3 wt% of porous material.
• the average particle size of the sample in this sol (O) measured by the dynamic light scattering method was 195 nm, and the converted specific surface area was 14 m 2 / g.
• the sol was dried at 105 ° C to obtain a porous material.
• the average pore diameter of this sample was 10 nm, and the pore volume was 1.06 ml Zg.
• the nitrogen adsorption specific surface area by the BET method was 590 m 2 Zg, and the difference from the reduced specific surface area was 576 m 2 / g.
• Observation of the primary particles of this sample from an electron micrograph revealed that the average particle diameter was 35 nm, The rod-shaped particles had an average particle length of 190 nm and an average aspect ratio of 5.4.
• the obtained sol (O) was used as a coating film.
• a pull mouth nick was extracted in the same manner as in Example 14 except that a polysulfone membrane SLP-1053 (manufactured by Asahi Kasei Corporation) was used instead of AHP-1010. Extraction was possible although the flux was lower than AHP-1010.
• a pull-mouth yuk was extracted in the same manner as in Example 14, except that ultrafiltration was performed at pH 4.0 without adding NaOH. In was concentrated to 2% S i 0 2 concentration, the flow rate was lowered, but the extraction was possible.
• the concentration of the pluronic P123 in 8 0000 g of the concentrated solution was 0.30%, and the concentration of the filtrate was 2700%.
• the Pluronic P 123 concentration in g was 0.27%.
• Example 17 when the pull-mouth nicks were concentrated using the polysulfone membrane SLP-1053, it took 150 minutes for the concentration. The water permeability after washing was 90% before use.
• Example 1 A sol (P) having a silica concentration of 7.2% by weight was obtained in the same manner as in Example 1, except that the active silica aqueous solution was added in an addition time of 3 seconds. Observation of the primary particles of this sample from electron micrographs revealed that the primary particles were rod-shaped particles with an average particle diameter of 30 nm, an average particle length of 5 O nm, and an average aspect ratio of 1.7. The obtained sol (P) was used as a coating film. table 1
• the porous substance of the present invention has fine pores and fine pores, it can be expected to have an effect of absorbing, wrapping and protecting the substance inside, and gradually releasing the substance, and further has transparency and smoothness. It can be applied to necessary fields.
• porous material of the present invention has a large average aspect ratio and microscopically filled particles, a large amount of the material can be easily held and the diffusion is fast.
• porous substance of the present invention By treating the porous substance of the present invention with a silane coupling agent, it is possible to produce a sol that is stable even in an acidic state or a cationic substance is added and that can withstand long-term storage. .
• the ink jet recording medium of the present invention has an excellent effect on ink absorption and transparency.

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• 2002
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